Absorbent Article Comprising Cyclodextrin Complexes

ABSTRACT

Disclosed are absorbent articles having a cyclodextrin complex of one or more odor controlling organic compounds wherein the cyclodextrin is a substituted cyclodextrin (wherein the H atom of OH groups in positions 2, 3 and 6 is partially or entirely replaced by a substituent —R) having a substitution degree (DS) of 0.4 or more —R substituents per molecule of cyclodextrin and wherein substitution in position 2 is 20% or above, in position 6 is 20% or above and in position 3 is 50% or below. Cyclodextrin complexes of this type release the odor controlling organic compound much faster and in more complete manner than non-substituted or differently substituted cyclodextrin complexes thus the odor control efficacy is improved.

FIELD OF THE INVENTION

The present invention relates to an absorbent article comprisingcyclodextrin complexes of odor controlling organic compounds, whereinthe cyclodextrin is a substituted cyclodextrin.

BACKGROUND OF THE INVENTION

Absorbent articles, according to the present invention, are articleswhich can be used to absorb any type of fluid. These articles includeabsorbent hygienic articles (like for example sanitary napkins,pantyliners, tampons, inter labial articles, adult incontinence articlessuch as adult incontinence pads, pants and diapers, baby pants anddiapers, breast pads and hemorrhoid pads). Other absorbent articles,according to the present invention, can be for example absorbent papertowels, wipes, toilet paper, or facial tissues as well as absorbentarticles used in the medical field such as wound dressings and surgicalarticles and absorbent articles used in food technology and conservation(such as fluid pads for meat, fish and so on). Absorbent articles,according to the present invention, encompass also absorbent materialsused industrially to absorb fluids (for example, to contain spillage ofchemicals in fluid form).

Absorbent hygienic articles are commonly used to absorb, and in somecases, retain bodily fluids and other exudates excreted by the human oranimal body, such as urine, menses, blood, fecal materials or mucus orchemicals or any type of fluid waste. Paper towels, wipes, facialtissues, toilet paper, and other absorbent articles may be used also toabsorb kitchen and food residues and/or any kind of dirt or waste. Inmany cases, the absorbed materials can be malodorants or can generatemalodors with time while the article is still being used, or after ithas been disposed of or thrown in the trash.

Materials for controlling and reducing malodors in absorbent articleshave been identified in the art. Odor absorbers (such as activatedcarbon, zeolites, silica and the like) have been widely used to trapvolatile malodorant molecules in porous solids. Also, uncomplexedcyclodextrin molecules have been used to trap malodorant molecules bycomplexing them, and thus reducing their volatility therefore actingsimilarly to odor absorbers.

However, the action of odor absorbers is not always satisfactory, sothat in the art they have been complemented or replaced by odorcontrolling organic compounds which play an active role in reducing theperception of malodors. Among these odor controlling organic compounds,fragrances (i.e. chemicals or blends of chemicals which stimulate theolfactory receptors providing a pleasant smell), odor masking compounds(i.e. compounds which stimulate the olfactory receptors so thatunpleasant odors are perceived less or perceived as less disturbing),and reactive compounds (i.e. compounds which chemically react with themalodorant molecules altering their nature) are known and have beendescribed e.g. in patent applications published under number EP1886698,EP2114331 EP2468308 EP3010555 EP3010554 EP3010553, all assigned to theProcter & Gamble Company.

It is also known from the art cited above, that these odor controllingorganic compounds can be introduced into the absorbent articles in theform of complexes with cyclodextrin. This is beneficial in some cases,because fragrances and odor masking compounds are, by definition,volatile materials and therefore tend to evaporate from the absorbentarticles during storage and use, thus losing efficacy. Most reactivecompounds are also volatile, so the formation of cyclodextrin complexesprevents their evaporation as well. Moreover, all reactive compounds(volatile and less volatile) being “reactive”, they tend to have poorchemical stability. The formation of cyclodextrin complexes alsoprotects the reactive molecules from unwanted reactions, greatlyimproving their chemical stability during storage and usage of theabsorbent articles.

When odor controlling organic compounds are incorporated into absorbentarticles in the form of cyclodextrin complexes, they are typicallyreleased from the cyclodextrin complexes when the article comes intocontact with the fluids to be absorbed. This is typically the moment atwhich malodors can start developing and at which the release of odorcontrolling compounds is more necessary. This has also been described inthe documents cited above.

Known cyclodextrin complexes are relatively effective in releasing thecomplexed odor controlling organic compounds, however, an aspect wherean improvement can still be beneficial is improving the kinetics and thecompleteness of the release. As mentioned above, the need forcontrolling malodors typically occurs at the exact moment when a fluidis absorbed into the article (e.g. urine or menstrual fluids in hygienicarticles, blood from food preparation absorbed by a paper towel and soon). Current cyclodextrin complexes, although very efficient, stillrequire a certain amount of time to release the odor controllingcompounds, and therefore in some cases, it is possible that malodors canbe perceived (even if only for a short time) between the moment thefluid is absorbed and the moment when the odor controlling compounds arereleased.

The perception of menstrual or urine malodor when wearing an absorbentarticle is clearly unwanted, even if only for a short time, and it cancause embarrassment and loss of personal confidence. There is also ahigh demand for technologies which counteract malodors in the fastestpossible way in the kitchen and among medical uses.

Based on the foregoing, what is needed is an absorbent article whichutilizes an improved odor control composition, facilitated applicationof odor control composition, and/or improved placement of the odorcontrol composition within the absorbent article.

SUMMARY OF THE INVENTION

The present invention relates to absorbent articles comprising acyclodextrin complex of one or more odor controlling organic compounds,wherein said cyclodextrin is a substituted cyclodextrin (wherein the Hatom of OH groups in positions 2, 3 and 6 is partially or entirelyreplaced by a substituent —R) having a substitution degree (DS) of 0.4or more —R substituents per molecule of cyclodextrin and whereinsubstitution in position 2 is 20% or above, in position 6 is 20% orabove and in position 3 is 50% or below.

The present invention also encompasses a method to manufacture anabsorbent article the method comprising:

-   -   providing a solution in a solvent system said solution        comprising a substituted cyclodextrin as described above and an        odor controlling organic compound,    -   applying an amount of the solution to one of the layers making        up the absorbent article and preferably evaporating the solvent        so to precipitate the cyclodextrin complex.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph depicting a representative chromatogram of hydrolyzed,reduced, and acetylated methyl β-cyclodextrin.

FIG. 2 is a graph depicting the release effectiveness among severalcyclodextrin complexes.

FIG. 3 is a chart depicting the total perfume release from MBCD coatedonto various components of a diaper.

FIG. 4 is a graph depicting the GC-MS signal peak areas of perfumematerials emanating from dry versus wetted AGM, which possesses MBCDcoated on the AGM surface or incorporated within the AGM particle

FIG. 5 is a schematic illustration of an absorbent article.

DETAILED DESCRIPTION OF THE INVENTION

The present invention pertains to cyclodextrin complexes comprisingposition-specific-substituted cyclodextrins comprising one or more odorcontrolling compounds, hereafter, “substituted cyclodextrin complexes.”The position-specific-substituted cyclodextrins described hereincomprises various degrees of substitution in the 2, 3, and 6 positions.As discussed herein, position-specific-substituted cyclodextrins withsubstitution in positions 2 and 6 provide benefits over conventionalβ-cyclodextrins and over completely substituted cyclodextrins, i.e.substitution in positions, 2, 3, and 6. There are many benefits toutilizing position-specific-substituted cyclodextrins. For example,position-specific-substituted cyclodextrins have a higher solubilitythan their conventional β-cyclodextrin counterparts. The increasedsolubility can provide more rapid release of encapsulated fragrances inthe position-specific-substituted cyclodextrin. Also, with the increasedsolubility, less moisture may be required to liberate encapsulatedfragrances in the position-specific-substituted cyclodextrin. Thisincreased solubility can also mean that lessposition-specific-substituted cyclodextrin may be utilized in absorbentarticles than their β-cyclodextrin counterparts.

Because of the increased solubility of the position-specific-substitutedcyclodextrins, there are methods of application of theposition-specific-substituted cyclodextrins which are not available fortheir conventional β-cyclodextrin counterparts. With the new methods ofapplication, the position-specific-substituted cyclodextrins may beprovided to areas of the absorbent article which may not have beenpossible with their conventional β-cyclodextrin counterparts.Additionally, the position-specific-substituted cyclodextrins canprovide higher efficacy than their conventional β-cyclodextrincounterparts.

The aforementioned benefits of utilizing position-specific-substitutedcyclodextrins are discussed in additional detail herein.

“Absorbent article” refers to articles that absorb any type of fluid.These articles are typically disposable and include paper towels, wipes,toilet paper, facial tissue, absorbent articles used in the medicalfield such as wound dressings and surgical articles, absorbent articlesused in food technology and conservation (such as fluid pads for meat,fish and the like), absorbent articles used industrially to absorbfluids, for example to contain spillage of chemicals in fluid form andabsorbent hygienic articles. The term “absorbent hygienic articles”refers to devices that absorb and contain body exudates, such as urine,menses, blood and feces. The term “disposable” is used herein todescribe absorbent articles which are not intended to be laundered orotherwise restored or reused as an absorbent article after a single use.Examples of absorbent hygienic articles include diapers, toddlertraining pants, adult incontinence pants, pads or diapers, and femininehygiene garments such as sanitary napkins, pantiliners, tampons,interlabial articles, breast pads, hemorrhoid pads, and the like.

Absorbent hygienic articles and components thereof, including atopsheet, backsheet, absorbent core, and any individual layers of thesecomponents, can have a body-facing surface and a garment-facing surface.As used herein, “body-facing surface” means that surface of the articleor component which is intended to be worn toward or adjacent to the bodyof the wearer, while the “garment-facing surface” is on the oppositeside and is intended to be worn toward or placed adjacent to thewearer's undergarments when the disposable absorbent article is worn.

Most absorbent hygienic articles of the present invention (except thosefor internal use such as tampons) typically comprise a topsheet, abacksheet, and an absorbent core disposed between the topsheet andbacksheet.

Absorbent articles of the present disclosure may utilize improved odorcontrol compositions, facilitated application of odor controlcompositions, and/or improved placement of the odor control compositionswithin the absorbent article. For example, it has been surprisinglyfound that by selecting the cyclodextrin molecule forming the complexwith the odor controlling organic compounds fromposition-specific-substituted cyclodextrin (wherein the H of some OHgroups is replaced by a substituent —R) having a substitution degrees of0.4 or more —R groups per glucose unit and wherein substitution inposition 2 is 20% or above, in position 6 is 20% or above and inposition 3 is less than the substitution percentage of position 2 and/orposition 6, the kinetic and the completeness of the release aresignificantly improved. Additional benefits of utilizingposition-specific-substituted cyclodextrins are discussed in additionaldetail herein.

Topsheet

The topsheet of the absorbent hygienic article is preferably compliant,soft feeling, and non-irritating to the wearers skin and hair. Further,the topsheet is liquid pervious, permitting liquids (e.g., menses and/orurine) to readily penetrate through its thickness. A suitable topsheetmay be manufactured from a wide range of materials such as woven andnonwoven materials (e.g., a nonwoven web of fibers), polymeric materialssuch as apertured formed thermoplastic films, apertured plastic films,and hydroformed thermoplastic films, porous foams, reticulated foams,reticulated thermoplastic films; and thermoplastic scrims. Suitablewoven and nonwoven materials can be comprised of natural fibers (e.g.,wood or cotton fibers), synthetic fibers (e.g., polymeric fibers such aspolyester, polypropylene, or polyethylene fibers) or from a combinationof natural and synthetic fibers. When the topsheet comprises a nonwovenweb, the web may be manufactured by a wide number of known techniques.For example, the web may be spunbonded, carded, wet-laid, melt-blown,hydroentangled, combinations of the above, or the like.

In some forms, the topsheet may be a laminate of two or more materials,e.g. including a nonwoven and a film. In such forms, the nonwoven mayform a body-facing surface of the topsheet. Or, the film may form atleast a portion of the body-facing surface of the topsheet. Films foruse as topsheets are discussed in U.S. Pat. Nos. 4,629,643; 5,460,623;and. 6,563,013. Additional examples of formed films suitable for use asa topsheet or a portion thereof are described in U.S. Pat. No.3,929,135, issued to Thompson on Dec. 30, 1975; U.S. Pat. No. 4,324,246,issued to Mullane et al. on Apr. 13, 1982; U.S. Pat. No. 4,342,314,issued to Radel et al. on Aug. 3, 1982; U.S. Pat. No. 4,463,045, issuedto Ahr et al. on Jul. 31, 1984; U.S. Pat. No. 5,006,394, issued to Bairdon Apr. 9, 1991; U.S. Pat. No. 4,609,518, issued to Curro et al. on Sep.2, 1986; and U.S. Pat. No. 4,629,643, issued to Curro et al. on Dec. 16,1986.

Nonlimiting examples of woven and nonwoven materials suitable for use asthe topsheet or a portion thereof include fibrous materials made fromnatural fibers, modified natural fibers, synthetic fibers, orcombinations thereof. These fibrous materials can be either hydrophilicor hydrophobic, but it is preferable that the topsheet be hydrophobic orrendered hydrophobic. Some suitable nonwoven materials suitable for useas a topsheet are described in U.S. Pat. Nos. 5,792,404 and 5,665,452.

Backsheet

The backsheet can be impervious to liquids (e.g., menses and/or urine)and can be preferably manufactured from a thin plastic film, althoughother flexible materials may also be used such as nonwovens. As usedherein, the term “flexible” refers to materials which are compliant andwill readily conform to the general shape and contours of the humanbody. The backsheet can prevent the exudates absorbed and contained inthe absorbent core from wetting articles which contact the absorbentarticle such as bedsheets, pants, pajamas and undergarments. Thebacksheet can also be vapor permeable (“breathable”), while remainingfluid impermeable. The backsheet may comprise a woven or nonwovenmaterial, polymeric films such as thermoplastic films of polyethylene orpolypropylene, or composite materials such as a film-coated nonwovenmaterial.

The backsheet can comprise panty fastening means applied on its surface,particularly the surface facing outside the absorbent article in orderto allow the article to stay in place when worn between the user'scrotch and panties. Such panty fastening means can be for example alayer of adhesive or mechanical means such as Velcro® or combinationthereof. When an adhesive is present, typically a release paper is alsopresent in order to protect the adhesive before use.

The backsheet and the topsheet can be positioned respectively adjacentthe garment surface and the body surface of the absorbent core. Theabsorbent core can be joined with the topsheet, the backsheet, or bothin any manner as is known by attachment means, such as those well knownin the art. Embodiments of the present invention are envisioned whereinportions of the entire absorbent core are unattached to either thetopsheet, the backsheet, or both.

Absorbent Core

The absorbent core can be formed from any of the materials well known tothose of ordinary skill in the art. Examples of such materials includemultiple plies of creped cellulose wadding, fluffed cellulose fibers,wood pulp fibers also known as airfelt, textile fibers, a blend offibers, a mass or batt of fibers, airlaid webs of fibers, a web ofpolymeric fibers, and a blend of polymeric fibers. Other suitableabsorbent core materials include absorbent foams such as polyurethanefoams or high internal phase emulsion (“HIPE”) foams. Suitable HIPEfoams are disclosed in U.S. Pat. No. 5,550,167, U.S. Pat. No. 5,387,207,U.S. Pat. No. 5,352,711, and U.S. Pat. No. 5,331,015. Other suitablematerials for use in absorbent cores comprise open celled foams orpieces thereof. The use of foams in absorbent cores is described inadditional detail in U.S. Pat. Nos. 6,410,820; 6,107,356; 6,204,298;6,207,724; 6,444,716; 8,211,078, and 8,702,668.

In some forms, the absorbent core structure may comprise a heterogeneousmass layer or may utilize methods or parameters such as those describedin U.S. patent application Ser. No. 14/715,984, filed May 19, 2015; U.S.patent application Ser. No. 14/750,399, Jun. 25, 2015; U.S. patentapplication Ser. No. 14/751,969 filed Jun. 26, 2015; U.S. patentapplication Ser. No. 15/078,132 filed Mar. 23, 2016; U.S. patentapplication Ser. No. 14/750,596 filed Jun. 25, 2015; U.S. patentapplication Ser. No. 15/084,902 filed Mar. 30, 2016; U.S. patentapplication Ser. No. 15/343,989 filed Nov. 4, 2016; U.S. patentapplication Ser. No. 15/344,273 filed Nov. 4, 2016; U.S. patentapplication Ser. No. 15/344,294 filed Nov. 4, 2016; U.S. patentapplication Ser. No. 14/704,110 filed May 5, 2015; U.S. patentapplication Ser. No. 15/194,894 filed Jun. 28, 2016; U.S. patentapplication Ser. No. 15/344,050 filed Nov. 4, 2016; U.S. patentapplication Ser. No. 15/344,117 filed Nov. 4, 2016; U.S. patentapplication Ser. No. 15/344,177 filed Nov. 4, 2016; U.S. patentapplication Ser. No. 15/344,198 filed Nov. 4, 2016; U.S. patentapplication Ser. No. 15/344,221 filed Nov. 4, 2016; U.S. patentapplication Ser. No. 15/344,239 filed Nov. 4, 2016; U.S. patentapplication Ser. No. 15/344,255 filed Nov. 4, 2016; U.S. patentapplication Ser. No. 15/464,733 filed Nov. 4, 2016; U.S. ProvisionalPatent Application No. 62/437,208 filed Dec. 21, 2016; U.S. ProvisionalPatent Application No. 62/437,225 filed Dec. 21, 2016; U.S. ProvisionalPatent Application No. 62/437,241 filed Dec. 21, 2016; or U.S.Provisional Patent Application No. 62/437,259 filed Dec. 21, 2016. Theheterogeneous mass layer has a depth, a width, and a height.

In some forms, a combination of absorbent core materials may beutilized. For example, forms are contemplated where a first layer of anabsorbent core comprises a foam material or pieces thereof as describedpreviously, and a second layer of an absorbent core comprises an airlaidmaterial. Such combinations are described in U.S. Patent Publication No.2014/0336606 and U.S. Pat. No. 9,649,228.

For some absorbent articles, the absorbent core can be relatively thin,less than about 5 mm in thickness, or less than about 3 mm, or less thanabout 1 mm in thickness. Thickness can be determined by measuring thethickness at the midpoint along the longitudinal centerline of the padby any means known in the art while under a uniform pressure of 1.72kPa.

The absorbent core can comprise superabsorbent materials such asabsorbent gelling materials (AGM), including AGM fibers, as is known inthe art. The absorbent core can therefore constitute a layer comprisingsuperabsorbent material.

The absorbent article can comprise other additional components, forexample between the topsheet and absorbent core, such as a secondarytopsheet or acquisition layer. The secondary topsheet or acquisitionlayer can comprise a tissue layer or a nonwoven, such as cardedresin-bonded nonwovens, embossed carded resin-bonded nonwovens,high-loft carded resin-bonded nonwovens, carded through-air bondednonwovens, carded thermo-bonded nonwovens, spunbonded nonwovens, and thelike. A variety of fibers can be used in the secondary topsheet oracquisition layer, including natural fibers, e.g. wood pulp, cotton,wool, and the like, as well as biodegradeable fibers, such as polylacticacid fibers, and synthetic fibers such as polyolefins (e.g.,polyethylene and polypropylene), polyesters, polyamides, syntheticcellulosics (e.g., RAYON®, Lyocell), cellulose acetate, bicomponentfibers, and blends thereof. The basis weight of the secondary topsheetor acquisition layer can vary depending upon the desired application. Insome forms, the secondary topsheet or acquisition layer may comprise asuper absorbent polymer, e.g. AGM deposited thereon. In such forms, thesecondary topsheet or acquisition layer may comprise a first AGM whilethe absorbent core comprises a second AGM. In some forms, the first AGMmay be different than the second AGM.

The absorbent article can comprise further components such as sidecuffs, typically found in diapers, or side wings or side flaps,typically found in sanitary napkins.

Absorbent catamenial tampons are absorbent articles for internal use inthe vagina which are typically made by a pledget comprising absorbentfibers compressed to a cylindrical shape. Tampons can be “digitaltampons” when they have a self-sustaining shape and can be inserted witha finger or “applicator tampons” i.e. tampons which are introduced usingan applicator. Tampons can also comprise an extraction cord so tofacilitate extraction from the vagina.

Absorbent hygienic articles herein are often commercialized in packagescontaining a plurality of units, often the package is a plastic film ora carton box. Single units contained within the commercial package canbe individually packaged or not.

Additional Layers

In some forms, the absorbent articles of the present disclosure maycomprise additional layers disposed between the topsheet and theabsorbent core and/or between the absorbent core and the backsheet. Someexamples include a secondary topsheet, acquisition layer, and/ordistribution layer which can be disclosed between the topsheet and theabsorbent core. Other examples include distribution layers orliquid-impermeable layers which are disposed between the absorbent coreand the backsheet.

Structure of Substituted Cyclodextrin Complex

For “complex”, it is intended to mean an “inclusion complex” within themeaning of IUPAC Compendium of Chemical Terminology 2nd Edition (1997),wherein the complexing agent (the cyclodextrin in this case) is the hostand the complexed compound is the “guest”.

As known, cyclodextrins are a family of compounds where a number ofglucose units are bound together in a ring shaped structure (cyclicoligosaccharides). More specifically cyclodextrins are formed by 5 ormore α-D-glucopyranoside units connected through the glycosidic linkagesin positions 1 and 4 on the glucose ring. Typically, the number ofglucose units forming each ring is from 6 to 12 and the most commonforms are those with 6, 7 or 8 glucose units also calledalpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin respectively.

In all cyclodextrins, each glucose units has three OH groups bound tothe carbon atoms in positions 2, 3 and 6. As mentioned previously, theinventors have surprisingly found that the utilization ofposition-specific-substituted cyclodextrins provides benefits over theirβ-cyclodextrin and completely substituted counterparts.

As used herein, the term “position-specific-substituted cyclodextrin”includes any cyclodextrin wherein one or more hydrogen atom of the OHgroups in positions 2 and 6 of the glucose units is replaced by asubstituent —R thus forming an —OR group. Similarly, as used herein, theterm “completely substituted cyclodextrin” includes any cyclodextrinwherein each of the OH groups in positions 2, 3, and 6 have beenreplaced by OR groups. The average number of —R substituents for eachglucose unit in a given sample represents the “degree of substitution”(DS) which is a number ranging from 0 to 3 where 0 corresponds to nosubstitutions (all OH groups in position 2, 3 and 6 are present) and 3to a complete substitution (all OH groups in position 2, 3 and 6 arereplaced by OR groups). The average is calculated on a molar basis.

The absorbent articles of the present invention comprise substitutedcyclodextrin complexes of one or more odor controlling organic compound,wherein the substituted cyclodextrin complex comprisesposition-specific-substituted cyclodextrins. The substitutedcyclodextrin complex has a substitution degree (DS) of 0.4 or more —Rsubstituents per molecule of cyclodextrin and wherein substitution inposition 2 is 20% or above, in position 6 is 20% or above.

In some forms of the invention, the average degree of substitution canbe between 0.4 and 2.5, between 0.9 and 2.4, between 1.2 and 2.2,between 1.6 and 2.1, specifically reciting all values within theseranges and any ranges created thereby. In some forms of the invention,the substitution in position 2 can be between 20 and 90%, morepreferably between 45% and 80%. In some forms of the invention, thesubstitution in position 6 can be between 20 and 90%, more preferablybetween 45% and 80%. In some forms, the invention may encompasscombinations of the preferred aspects mentioned above.

It is worth noting that position-specific-substituted cyclodextrins aresynthesized from conventional cyclodextrins. Via this synthesis, avariety of cyclodextrin molecules are created. For example, some of thecyclodextrin molecules may not be substituted at all, i.e. all OH groupsin positions 2, 3, and 6 are present. As another example, some of thecyclodextrin molecules will be substituted as desired, i.e.position-specific-substituted cyclodextrins. And, as another example,some of the cyclodextrins will experience complete substitution, i.e.all OH groups are substituted in positions 2, 3, and 6 by OR groups.However, as discussed herein, the position-specific-substitutedcyclodextrins, with substitution in positions 2 and 6, providesadditional benefits over the completely substituted cyclodextrins. Assuch, forms of the present invention are contemplated where the degreeof substitution in position 3 is less than the level of substitution inposition 2 and/or position 6. In some forms, the degree of substitutionin position 3 is less than about 50 percent, less than about 40 percent,less than about 30 percent, less than about 20 percent, or less thanabout 10 percent, specifically reciting all values within these rangesand any ranges created thereby.

The —R substituents in the —OR groups can be selected from anysubstituent having a carbon atom in position 1 (thus forming an —O—C—bond with the oxygen atom). Suitable —R substituents may include carbonatoms chains which are saturated or unsaturated and can be straight orbranched. For example, suitable —R substituents include saturated andstraight chain C1-6 alkyl, hydroxyalkyl, and mixtures thereof.Particularly suitable —R substituents have a carbon chain of from 1 to 6carbon atoms and are selected from alkyl, hydroxyalkyl, dihydroxyalkyl,carboxy-alkyl, aryl, maltosyl, allyl, benzyl, alkanoyl, and mixturesthereof, wherein the term “alkyl” encompasses both linear and branchedalkyl chains.

In some forms, an —R substituent may comprise propyl, ethyl, methyl, andhydroxypropyl. Different —R substituents can be present in the sameposition-specific-substituted cyclodextrin sample on the samecyclodextrin molecule and even on the same cyclodextrin glucose unit.

In one particular form, all the —R substituents may be methylsubstituents. In this case, the cyclodextrin is also called “methylatedβ-cyclodextrin”. For example, a particularly suitable cyclodextrinmaterial for the present invention is a methylated cyclodextrin having aDS of 0.4 or higher, preferably from 0.4 to 2.5, more preferably between0.9 and 2, even more preferably between 1.2 and 1.8 and wherein at least20%, preferably between 20% and 90%, more preferably between 45% and 80%of the —OH groups in positions 2 and 6, respectively, are methylated.

The degree of substitution can be measured with gas chromatography asdescribed below, with reference to methyl substituents inβ-Cyclodextrin.

It has been surprisingly found that substituted cyclodextrin complexes,according to the present invention, release more rapidly the odorcontrolling organic compound when the absorbent article is contactedwith an aqueous fluid, compared with similar complexes wherein thecyclodextrin does not comprise position-specific-substitutedcyclodextrins or where the substitution is distributed between positions2, 3 and 6.

In general, cyclodextrin complexes, including substituted cyclodextrincomplexes, can help prevent the evaporation of the complexed fragrancecompounds. In use, moisture from urine or menses contacts thecyclodextrin complex and dissolves the crystalline structure of thecyclodextrin complex. This causes the release of the fragrance materialswithin the cyclodextrin complex. However, a problem exists whenincorporating a cyclodextrin complex in an absorbent hygienic article.Other components, such as the absorbent core and/or superabsorbentmaterial, of the absorbent article have a strong affinity for bodilyfluids, e.g. menses and urine, including the moisture contained therein.So, when an absorbent article is insulted with bodily fluid, such asmenses or urine, the cyclodextrin complex can be in competition with theabsorbent core and/or superabsorbent material for the moisture containedin the bodily fluid. The absorbent core and/or superabsorbent materialhas a strong affinity for the moisture and once the absorbent coreand/or superabsorbent material contacts the bodily fluid, the absorbentcore and/or superabsorbent material effectively “lock-up” the moistureof the bodily fluid, thereby reducing the amount of moisture availableto contact the cyclodextrin complex. So, only a limited amount ofmoisture may be available to dissolve the cyclodextrin crystallinestructure and release the fragrance compounds to provide odor controlbenefits.

With conventional cyclodextrin complexes, a larger amount of moisturemay be required to solubilize the cyclodextrin molecules and release theencapsulated fragrance. The same holds true for completely substitutedcyclodextrins where positions 2, 3, and 6 are substituted. However, theinventors have surprisingly found that with the use of aposition-specific-substituted cyclodextrins, as described herein, lessmoisture may be required to solubilize the position-specific-substitutedcyclodextrins. So, more of the complexed fragrance compounds may bereleased without compromising the absorbent or retention capacity of theabsorbent article.

Determination of Methyl Substituent Distribution

The Methyl Substituent Distribution in Methylated β-Cyclodextrin(hereafter “MBCD”) is measured using gas chromatograph withsplit/splitless injection and flame ionization detection (a suitableinstrument is the Agilent 7890B GC available from Agilent, Santa Clara,Calif., or equivalent). The β-cyclodextrin is hydrolyzed, reduced andthen acetylated for analysis. Additionally, gas chromatography/massspectrometry (a suitable unit is the 5777A Mass Selective Detector (MSD)also available from Agilent, or equivalent) can be used to identify theacetylated products to confirm peak identity. Both instruments arecalibrated and operated as per the manufacturer's instructions.

Derivatization reagents must be used with a purity of greater than orequal to 99%, except for the borohydride (98%), and can be obtained fromSigma Aldrich, or equivalent. Fifty mg of MBCD and 5 mL of 2 Mtrifluoroacetic acid solution were added to a 50 mL round bottom flaskwith magnetic stir bar. The reaction vessel was fitted with a watercooled condenser and heated to reflux for 4 hours while stirring. Aftercomplete hydrolysis, the reaction mixture was evaporated under vacuum todryness. Next, the hydrolysis product, 10 mL of ammonium hydroxide (32%in water), and 101 mg sodium borohydride (2.67 mmols) were stirred in a50 mL round bottom flask at 40° C. for 2 hours. Residual sodiumborohydride was quenched via dropwise addition of glacial acetic aciduntil the solution pH was in the range of 4.5 to 6. The resulting boricacid was removed via sequential additions of methanol (4×20 mL) to thereaction mixture, followed by evaporation under vacuum at 40° C. Thereaction product, 10 mL of pyridine, 36 mg of 4-dimethylaminopyridine(0.2947 mmols), and 630 μL acetic anhydride (630 μL, 6.6794 mmols) wereadded to a 50 mL round bottom flask with magnetic stir bar. The reactionwas stirred vigorously at room temperature for 20 hours. The acetylatedalditol products were extracted with 10 mL chloroform using a 60 mLseparatory funnel and washed three times with 10 mL of deionized water.The chloroform extract was diluted (1:3) with chloroform, and sampledfor gas chromatography analysis.

The GC analysis was performed on a 30 m long by 0.250 mm inner diametercolumn with 5% phenyl arylene methylpolysiloxane phase at a 1 μm filmthickness (a suitable column is the DBSMS available from Agilent, orequivalent USP G27 phase). The GC inlet was set at 280° C. in Split mode(5:1 split, glass wool packed liner) with a 3 mL septum purge. A 1.5mL/minute column flow of helium was set at an oven temperature of 150°C. under constant flow conditions. The detector was set at 300° C. withflows set to the instrument manufacturer's recommended conditions. TheGC oven was programmed to begin at 150° C. for 1 min, then ramp at 15°C./min to 250° C., hold for 4 min at 250° C., then ramp at 10° C./min to315° C. and a final hold of 1 min. 1 μL of the chloroform extract isinjected for analysis. A representative chromatogram of MBCD (CAVASOL®W7 M from Wacker Chemie AG) is given in FIG. 1. It is understood thatone skilled in the art can slightly modify the chromatographicconditions to achieve the necessary separation as needed.

GC-MS analysis is performed under the same chromatographic conditions asfor the flame ionization detection (FID). The temperature for the MSDtransfer line and detector were set to 280° C. and 300° C. respectively.The MSD was configured for electron ionization at −70 eV scanning from35 m/z to 400 m/z with a scan rate of 257 msec/scan. The Total IonChromatogram was evaluated using the fragmentation data in Table 1 toassign retention order of the glucitol products. The retention order wasthen applied to the GC-FID chromatograms.

For quantification, each peak measured by GC-FID that is associated witha glucitol monomer is integrated to give a peak area. The areas are thenused in Equations 1 and 2 to calculate the mole percent (mol %) of eachglucitol monomer and reported to the nearest 0.1 mol %. The results fromthe example chromatogram in FIG. 1 are given in Table 1.

$\begin{matrix}{{{mols}\mspace{14mu} {glucitol}\mspace{14mu} A} = {{mg}\mspace{14mu} \beta \mspace{14mu} {cyclodextrin} \times \frac{{FID}\mspace{14mu} {area}\mspace{14mu} {counts}\mspace{14mu} {for}\mspace{14mu} {glucitol}\mspace{14mu} A}{\sum{{FID}\mspace{14mu} {area}\mspace{14mu} {counts}\mspace{14mu} {of}\mspace{14mu} {all}\mspace{14mu} {glucitol}\mspace{14mu} {monomers}}} \times \frac{1}{M\; W_{A}}}} & {{Eq}.\mspace{14mu} 1}\end{matrix}$

where MW_(A) is the molecular weight of the acetylated glucitol

and mg β-cyclodextrin is the starting mass of underivatized MBCD.

$\begin{matrix}{{{mols}\mspace{14mu} \% \mspace{14mu} {glucitol}\mspace{14mu} A} = {\frac{{mols}\mspace{14mu} {glucitol}\mspace{14mu} A}{\sum{{mols}\mspace{14mu} {of}\mspace{14mu} {all}\mspace{14mu} {glucitol}\mspace{14mu} {monomers}}} \times 100\%}} & {{Eq}.\mspace{14mu} 2}\end{matrix}$

Additionally, the mol % of particular substitutions are calculated byaddition of the individual mol %. For example, mol % of all glucitolsmethylated at the 6 position (denoted in Table 1 as X6) would be the sumof the mol % of S2,6, S3,6 and S2,3,6.

The average degree of substitution was calculated according to Equation3. Mol % for all glucitol monomers sharing the same number of methylsubstituents (0, 1, 2, or, 3) were summed, multiplied by theirrespective methyl substituent number (0, 1, 2, or 3) and divided by 100.The result is reported to the nearest 0.1 mol %.

$\begin{matrix}{{{DS}\mspace{14mu} {per}\mspace{14mu} {glucose}\mspace{14mu} {unit}} = {\frac{1}{100}{\sum\limits_{i = 0}^{3}\; {{i \cdot {mol}}\mspace{14mu} \% \mspace{14mu} x}}}} & {{Eq}.\mspace{14mu} 3}\end{matrix}$

Where mol % x is equal to the summation of glucitol monomers having samenumber of methyl groups.

Data from a gas chromatogram of acetylated D-glucitol derivativesprepared from MBCD using the procedure described above is provided inTable 1. Table 1 shows Selected Fragments of Ionized D-Glucitol Acetateswhile FIG. 1 is an FID trace.

TABLE 1 m/z Compound 99 113 117 129 145 157 159 161 189 217 231 233 261289 305 333 2,3,6-Tri-O-methyl-D-glucitol, 1,4,5- X X X X X X triacetate2,6-Di-O-methyl-D-glucitol, 1,3,4,5- X X X X X tetraacetate3,6-Di-O-methyl-D-glucitol, 1,2,4,5- X X X X X X X tetraacetate2,3-Di-O-methyl-D-glucitol, 1,4,5,6- X X X X X X X tetraacetate6-O-methyl-D-glucitol, 1,2,3,4,5- X X X X X X X X X pentaacetate2-O-methyl-D-glucitol, 1,3,4,5,6- X X X X X X pentaacetate3-O-methyl-D-glucitol, 1,2,4,5,6- X X X X X X X X pentaacetateD-glucitol hexaacetate X X X X X = Fragment present in mass spectra

Table 2 provides data of the substituent distribution for MBCD, theaverage degree of methylation of the O6 and O2 positions, and theaverage degree of substitution (DS) per glucose unit.

TABLE 2 Substituent Distribution mol % Unsubstituted 9.1 S2 21.9 S3 5.8S6 10.4 S2,3 13.7 S2,6 20.1 S3,6 6.1 S2,3,6 12.8 X6 49.5 X2 68.6 X3 38.5Avg. DS per Glusose Unit: 1.6

The position-specific-substituted cyclodextrins of the present inventioncan be prepared by using methods known in the art for the selectivemodifications of cyclodextrins. For example, by using methods describedby Khan et al. (Chem. Rev. 1998, 98, 1977-1996). Alternative synthesisroutes for the preparation of the position-specific-substitutedcyclodextrins of the invention are known to the chemists skilled in thefield and broadly described in literature. For example, U.S. Pat. No.5,710,268 and the textbooks “Advances in cyclodextrin chemistry” byWerz, Vidal, Guiou, Sollogoub, Matthieu, Wiley-VCH Verlag GmbH ed. 2014;and “Modern Synthetic Methods in Carbohydrate Chemistry: FromMonosaccharides to Complex Glycoconjugates”, Werz, Daniel B.; Vidal,Sebastian, eds, 2014 Wiley-VHC Verlag GmbH provide additional details.

Once the position-specific-substituted cyclodextrins is provided,substituted cyclodextrin complexes of odor controlling organic compoundswhich are active against malodors can be prepared as known in the artfor the known cyclodextrin complexes, for example using the kneadingmethod described in U.S. Pat. No. 5,571,782 and U.S. Pat. No. 5,543,157or, using the spray drying method described in WO2008/104690A2.

Substituted Cyclodextrin Complex Positioning

The substituted cyclodextrin complex of the present invention can bedisposed in various locations in the absorbent article. In all cases,the substituted cyclodextrin complex can be simply applied on a surfaceof the article using any application method. More specifically, in thecase of paper towels, wipes, toilet paper and facial tissues, thesubstituted cyclodextrin complex can be applied on any surface of any ofthe layers making up the article or be mixed with the fibers during themaking process.

In the case of absorbent hygienic articles, the substituted cyclodextrincomplex can be disposed on the garment-facing side or the body-facingside of the topsheet or absorbent core, or on the body-facing side ofthe backsheet. In some forms, the substituted cyclodextrin complex isdisposed on the absorbent core. In such forms, the substitutedcyclodextrin complex may be disposed on the body-facing side of theabsorbent core. The substituted cyclodextrin complex can also bedisposed on other components of the absorbent article, when present,such as the garment-facing side or body-facing side of a secondarytopsheet or acquisition layer. The substituted cyclodextrin complex canalso be mixed with any of the fibers or materials making up any of thelayers of the absorbent article.

In some forms, the substituted cyclodextrin complex of the presentinvention is disposed in the absorbent article in or on a layer that iscloser to the body-facing surface of the absorbent article than theabsorbent core or a layer comprising superabsorbent material (e.g.absorbent gelling material (“AGM”)). In general, the substitutedcyclodextrin complex needs to come into contact with moisture toeffectively release the compound.

Surprisingly, it has been discovered that if the substitutedcyclodextrin complex is coated onto the outside surface of the AGMparticle, that this can actually speed activation and release of thecomplexed fragrance compounds. Without being bound by theory, it isbelieved that the high solubility of the complexes of the presentinvention and the relatively slow kinetic absorption by the AGMparticles allow the complete dissolution of the complexes before the AGMgranule is able to compete for the liquid absorption. And, it isbelieved that the location of the substituted cyclodextrin complex onthe surface of the AGM granule provides for a complete release exactlywhen and where it may be needed i.e. where a possible malodorant liquidis present. This can result in a more effective release of the complexedodor controlling organic compounds and can provide for improved odorcontrol benefits.

Examples were created and tested with regard to efficacy of thesubstituted cyclodextrin complex of the present disclosure in variouslocations of an absorbent article. Data is provided with regard to thegraph of FIG. 3. Components of the absorbent article tested weretopsheet, acquisition layer (AQL), core cover, and AGM surface. Asshown, the executions of substituted cyclodextrin complexes disposed onthe topsheet and on the AGM surface were more effective than substitutedcyclodextrin complexes in the AQL and the core cover. These examples arediscussed in additional detail in the Test Procedures section herein.

Based on FIG. 3, forms of the present invention are contemplated where asubstituted cyclodextrin complex is applied to an absorbent article suchthat the substituted cyclodextrin complex provides a peak area ratio ofgreater than about at least 1.0. In another form, a substitutedcyclodextrin complex can be provided to an absorbent article such thatthe substituted cyclodextrin complex provides a peak area ratio ofgreater than about 1.5, greater than about 1.75, or greater than about2.0, specifically reciting all values within these ranges and any rangescreated thereby.

In FIG. 4, examples of swelled AGM versus dry AGM were comparedregarding their perfume release. The graph of FIG. 4 shows the peak areaof GC-MS signals for perfume materials release from MBCD encapsulatedperfume incorporated into AGM (swelled AGM) versus MBCD encapsulatedperfume coated onto AGM particles. MBCD was incorporated within AGMparticles of some examples and coated on other examples.

As shown, examples where MBCD was incorporated into the AGM particlewere found to exhibit negligible release of perfume materials uponwetting with water. In contrast, the AGM particles coated with MBCDreleased much more perfume than did the examples where MBCD wasincorporated into the AGM. As shown, the perfume intensity may be muchgreater for the MBCD coated AGM particles when wetted versus the MBCDcoated AGM particles when dry.

In some forms, the substituted cyclodextrin complex, e.g. MBCD, may beprovided in a target zone of an absorbent article. As shown in FIG. 5,the target zone 330 of an absorbent article 300 represents the area ofthe absorbent article of expected fluid insult. The absorbent article300 is shown having an overall longitudinal length generally parallel toa Y-axis and an overall lateral width generally parallel to an X-axis.The absorbent article 300 further comprises a thickness in a Z-direction(not shown) which is perpendicular to an X-Y plane created by the X andY axes.

As shown, the target zone 330 may be disposed between two outer zones335. In some forms, the target zone 330 may comprise about 60 percent ofthe overall longitudinal length (along a Y-axis) of the absorbentarticle 300 where each of the outer zones comprise about 30 percent orless of the overall length or less of the absorbent article 300. In someforms, the target zone 330 may comprise about 50 percent of the overalllength while the outer zones 335 comprise about 40 percent or less ofthe overall length of the absorbent article. In some forms, the targetzone 330 may extend from about more than 20 percent to less than about80 percent, more than about 30 percent to less than about 70 percent,more than about 40 percent to less than about 60 percent of the overalllength of the absorbent article 300, specifically including all valueswithin these ranges and any ranges created thereby.

Forms are contemplated where the target zone 300 extends along only aportion of the overall lateral width (along an X-axis) of the absorbentarticle 300. For example, in some forms, the target zone 330 may extendfor less than about 90 percent of the overall width of the absorbentarticle 300. As another example, the target zone 330 may extend for lessthan about 75 percent of the overall width of the absorbent article 300.Still in other forms, the target zone 330 may extend for less than about50 percent of the overall width of the absorbent article 300. As yetanother example, the target zone 330 may extend for about more than 10percent to less than about 90 percent, more than about 20 percent toless than about 80 percent, more than about 30 percent to less thanabout 70 percent of the overall width, specifically including all valueswithin these ranges and any ranges created thereby. In such forms, areasof the article outside of the target zone 330 may be sans thesubstituted cyclodextrin complex. Or in other forms, the target zone 330may comprise more substituted cyclodextrin complex than either of theouter zones 335.

In the case of catamenial tampons the substituted cyclodextrin complexcan be present on or in any component of the tampon, including theabsorbent compressed pledget forming the tampon body, the overwrap, andthe extraction cord. For example, it can be comprised in the tamponbody, or on the tampon surface or, if an overwrap is present, on eithersurface of the overwrap. In case a secondary mass of absorbent materialis present along the extension cord proximal to the extraction end ofthe tampon, the substituted cyclodextrin complex can be comprised withinthis secondary mass.

In all cases, the substituted cyclodextrin complex of the invention canbe applied on one of the layers making up the absorbent article inpowder form or can be incorporated into a liquid or semi-solid carrierand applied as a lotion. In this case, the substituted cyclodextrincomplexes can be dispersed in a carrier to form a dispersion, and thedispersion applied to the absorbent article. The carrier can be selectedfor example from the group consisting of polysiloxane oil, mineral oil,petrolatum, polyethylene glycol, glycerin and the like, and mixturesthereof. The carrier is preferably polysiloxane oil, such as a siliconeglycol copolymer (commercially available from Dow Corning as Dow Corning190 Fluid).

The dispersion can be applied using conventional glue applicationequipment such as a slot applicator, which can be used for stripedpatterns, or air assisted applicators for patterned applications (likespray, spiral, serpentine, fibrils, Omega®, Signature® and the like).Patterned applications may allow one to position the complex in a waythat it does not impact fluid acquisition (i.e. in a fem care articlethe material could not be applied in correspondence with the vaginalopening) and the pattern, having a large void space, allows fluidpenetration also on the sides. Also, patterned applications are helpfulbecause they allow a precise application so that it is easier to avoidcontact with the glue which connects the various layers of the absorbentarticle.

However, for substituted cyclodextrin complexes of the presentdisclosure, another method of application to an absorbent article isavailable, which is not available for conventional cyclodextrincomplexes. For substituted cyclodextrin complexes of the presentdisclosure, the complex may be formed directly in the site of theapplication. This is made possible by the fact thatposition-specific-substituted cyclodextrins, according to the invention,have an improved solubility both in water and in ethanol based solvents.This improved solubility allows one to prepare substituted cyclodextrincomplexes of the present disclosure in the site of application (e.g. ona layer of material which is part of an absorbent article). And again,such method may not be applicable with unsubstituted cyclodextrins orcompletely substituted cyclodextrins, which each have lower solubilitythan position-specific-substituted cyclodextrins.

For the application method of substituted cyclodextrin complexes, theposition-specific-substituted cyclodextrins may be solubilized in asolvent system. The solvent system may comprise at least 60%, at least80%, or at least 95% of volatile solvents, specifically reciting allvalues within these ranges and any ranges created thereby. Some suitableexamples of volatile solvents include water, C1-C8 alcohols, C1-C8ketone and aldehydes, C1-C8 hydrocarbons, supercritical fluids, or evencooled gases in fluid form such as ethanol or mixtures thereof, togetherwith the odor controlling organic compound forming a solution.

In some forms, the solvent system comprises less than 5%, less than1.0%, or less than 0.5%, specifically reciting all values within theseranges and any ranges created thereby, of any non-volatile solvent(s)having a C Log P value less than 3. It is believed that suchnon-volatile solvents can interfere negatively with the crystallizationof the CD complex.

In some forms, the viscosity of the solution is such that is easilypumpable or sprayable (if desired). For example, the viscosity may beless than 60 cp at 20° C. or less than 40 cp at 20° C., specificallyreciting all values within these ranges and any ranges created thereby,(Brooksfield viscosity, measured at 20 sec⁻¹ and spindle 40 mm SST HBST). Viscosity can be lowered by further diluting the solution. Ifsolutions are prepared ahead of time prior to use, and water is used incombination with Ethanol, then the ratio of water to ethanol should bechosen to prevent the formation of microbial growth in storage. In someforms, the ratio of ethanol to water is at least 4/6 by weight.

In some forms, the odor controlling organic compound and theposition-specific-substituted cyclodextrin are added to the solventsystem mixture at a molar ratio of between 0.25:1 to 4:1, a molar ratioof between 0.5:1 to 2:1, or a molar ratio of between 0.8:1 to 1.2:1,specifically reciting all values within these ranges and any rangescreated thereby. The resulting solution can be applied on any substratemaking up the absorbent article with any type of applicator for liquidcompositions e.g. with a drop applicator or a spray applicator. Afterapplication, upon evaporation of the volatile solvent, the complex issurprisingly formed in situ without the need of additional carriers forthe application, surprisingly and the degree of complexing achieved ishigh.

It is believed that when the solvent which dissolves the cyclodextrinderivative evaporates, the cyclodextrin derivative can crystallize intoa number of small microcrystals featuring different crystal shapes whichdo not stack thus allowing fluid to better penetrate and activate themwhen in use. Being formed in the presence of a fibrous substrate, thecrystals tend to entrap some fibers and therefore to bind to it. Thisbinding is advantageous because not only is loss of the odor controllingorganic compound prevented but also positioning and dosing isfacilitated as the complex forms and remains in the place where thesolution is applied.

It is further believed that conventional cyclodextrin complexes stackinto an ordered crystalline form—measurable by x-raycrystallography—which discourages liquid penetration into thecrystalline form. In contrast, the substituted cyclodextrin complexes ofthe present disclosure are believed to form an amorphous crystallinestructure which tends to be better suited for solubility.

Surprisingly, it has been discovered that by creating a di-substitutedcyclodextrin composition, where in the substitution occurs predominantlyin the 2 and 6 positions, the speed and completeness of release isdramatically increased of the odor control composition complexed in thecyclodextrin.

Without wishing to be bound by theory, it is believed that underivatizedcyclodextrin cavities may hydrogen bond and stack into highlycrystalline structures that prevent moisture from penetrating into thecavity and releasing the cavity contents. By replacing the hydroxylgroups on the top and bottom of the cavities (i.e. in the 2 and 6positions), this prevents the cavities from stacking and leads to a moreamorphous crystalline structure that can be more easily activated withmoisture. Additionally, it is believed that as many of the hydroxylgroups in the 3 position as possible should be retained to promote watersolubility. In some forms, the substituted cyclodextrin may have adimethyl composition predominantly substituted in the 2 and 6 positionswith a short chain hydrocarbon.

It may be important that during the manufacturing process, the volatilesolvent evaporates as much as possible before the products are sealedinto air tight plastic bags as it common for absorbent articles.Articles can be heated during manufacturing in order to facilitate theevaporation of the solvent, but this may not be necessary.

When the substituted cyclodextrin complex is introduced into theabsorbent article as a coating on AGM particles, the coating can beobtained by depositing and evaporating a solution comprising thecyclodextrin and the one or more odor controlling organic compound asdescribed above in the case of the application to any other layer ormaterial of the absorbent article. Also, any other known coating methodcan be used.

More precisely coated AGM granules can be obtained, directly during themanufacturing operation of the absorbent article by spraying orotherwise depositing a solution comprising the cyclodextrin and the oneor more odor controlling organic compounds dissolved in appropriatesolvents as described above (e.g. ethanol, water, and mixtures thereof)onto the surface of the AGM in the assembly line before or after itsapplication within the absorbent article (i.e. AGM can be treated withthe substituted cyclodextrin complex solution when still in the drum,before application to the absorbent article or after having beendeposited onto the absorbent article.

Alternatively, pre-coated AGM granules can be directly prepared inadvance, e.g. directly by the AGM supplier and directly dosed in themanufacturing of the absorbent article, with the additional advantage ofnot having to control the evaporation of the solvent during themanufacturing of the article, especially in case article is manufacturedat high speeds and then packaged in air tight packages as it is the casefor certain absorbent articles.

Any suitable method of coating or application to the outside surface isappropriate. One method is to spray or mist a solution of the dissolvedcyclodextrin, odor controlling organic compound(s) and appropriatesolvents as described above onto the dry AGM particle surface (in thiscase it may be advantageous if the moisture of the dry AGM particle isless than about 20% moisture, preferably less than 10% moisture).Another method is to coat the AGM particle using the same solution andequipment such as a Wurster spray coater, commonly used to applycoatings to the outside surface of particles. Another method is to spraya solution on to a moving bed of dry AGM particles using a mist or sprayapplicator capable of creating a droplet size less than about half thesize of AGM particle. Alternatively, effective coating of AGM particlescan also be obtained by rapidly dipping a bed of AGM particles into atank of a solution of the dissolved cyclodextrin, odor controllingorganic compound(s) and appropriate solvents as described above, andremove it immediately thereafter to coat the outside surface withoutswelling the AGM particle is another method of coating the AGMparticles. In all cases an appropriate drying step should follow usingtechniques which are common in the art. This said, forming coating onsolid particles is a known process so that a skilled person would havemany methods available in the common knowledge to achieve effectivecoating of the particles, as long as a method does not require the AGMparticles to be in a prolonged contact with a large amount of water orother fluids which would swell the particle, that coating method wouldbe suitable for obtained coated AGM particles according to theinvention. Suitable methods are discussed in additional detail in U.S.Patent Application Publication No. 62/405,470.

Generally, it is preferred to apply a coating that results in a perfumeto AGM weight ratio of between 1:100,000 to 1:1000 specifically recitingall values within these ranges and any ranges created thereby.

The one or more odor controlling compounds is typically comprised intoan absorbent article in an amount of from about 0.01 to about 1000milligrams per absorbent article, from about 0.1 to about 100 milligramsper absorbent article, or from about 0.1 to about 500 milligrams perabsorbent article, specifically reciting all values within these rangesand any ranges created thereby.

The recited milligrams per absorbent article are applicable in generalto any absorbent article, however absorbent articles can have verydifferent sizes and therefore may contain more or less of the one ormore odor controlling compounds, depending on need. Because of theeffectiveness of the odor control technology of the present disclosure,a lower level of odor controlling compounds can be used to achieveeffective odor control versus conventional odor control technologies asshown in Table 3 below.

For example, considering absorbent articles for personal hygiene thetypical amounts are shown in Table 3 (the weight indicated only refersto the one or more odor controlling compound and excludes to thecyclodextrin used to for the complex with it):

TABLE 3 Range (in mg) Absorbent article Min Max Panty-Liners 0.1 5Sanitary Napkins 0.2 20 Adult incontinence pads 0.5 30 Adultincontinence Diapers 1 50 Baby Diapers 1 50 Tissue paper (roll) 0.2 20

In some forms of the present invention, a substituted cyclodextrincomplex may comprise the one or more odor controlling compounds whichare provided in an absorbent article at the above levels. However, asdiscussed heretofore, substituted cyclodextrin complexes may have highersolubility than conventional cyclodextrin complexes. As such, a loweramount of the one or more odor controlling compounds may be utilized andstill deliver an effective amount of fragrance. Accordingly, forms ofthe present invention are contemplated where the one or more odorcontrolling compounds are provided in a substituted cyclodextrin and isprovided at less than about 90 percent of the levels of Table 3, at lessthan about 75 percent of the levels of Table 3, at less than about 60percent of the levels of Table 3, at less than about 50 percent of thelevels of Table 3, at less than about 35 percent of the levels of Table3, at less than about 25 percent of the levels of Table 3, greater thanabout 10 percent of the levels of Table 3, specifically including allvalues within these ranges and any ranges created thereby.

Any of the known odor controlling organic compound which form stablecomplexes with cyclodextrin can be used in the present invention, onlyone odor controlling organic compound can be used or more odorcontrolling organic compounds can be used in combination. Examples ofsuitable odor controlling organic compounds are mentioned here below inlists (a/a*), (b), (c), (d), and (e). It is in general preferred that atleast one reactive compound from lists (a/a*) or (b) is present.

List a) includes reactive compounds having a “thiol vapor pressuresuppression index” (TVPS) of more than 20.

Thiol Vapor Pressure Suppression (TVPS) index is a measure of thereduction in butanethiol concentration in the headspace by a compound,as measured using a fast GC instrument, the zNose 7100 (ElectronicSensor Technologies, Newbury Park, Calif.).

Examples of preferred reactive compounds which are suitable for thepresent invention and which have a TVPS higher than 20 are those of thefollowing list (a*), these compounds not only have a TVPS higher than 20but they also form complexes with cyclodextrin which are particularlystable and release the complexed materials when needed.

(a*): melonal, adoxal, trans-2-hexenal, ligustral, Floral Super,Florhydral, 5-methyl-2-thiophene-carboxaldehyde, hydratropic aldehyde,undecenal, 9-undecenal, 10-undecenal, trans-4-decenal, cis-6-nonenal,isocyclocitral, precyclemone b, (E)-2,(z)-6-nonadienal, undecylaldehyde, methyl-octyl-acetaldehyde, Lauric aldehyde, silvial, vanillin,floralozone.

All these compounds in list (a/a*) are particularly reactive towardmalodorant molecules containing Sulfur atoms (thiol type malodors,typically associated with protein degradation e.g. in menstrual fluids,feces, food etc).

Additional reactive aldehydes and/or ketones which can be advantageouslyused include the following listed in list (b): hexyl cinnamic aldehyde,alpha-amylcinnamic aldehyde, p-anisaldehyde, benzaldehyde, cinnamicaldehyde, cuminic aldehyde, decanal, cyclamen aldehyde,p-t-butyl-alpha-methyldihydrocinnamaldehyde,4-hydroxy-3-methoxycinnamaldehyde, vanillin isobutyrate,2-phenyl-3-(2-furyl)prop-2-enal, ethyl vanillin acetate, vanillinacetate, heptanal, lauryl aldehyde, nonanal, octanal,phenylacetaldehyde, phenyl propyl aldehyde, salycil aldehyde, citral,2,4-dihydroxy-3-methylbenzaldehyde, 2-hydroxy-4-methylbenzaldehyde,5-methyl salicylic aldehydes, 4-nitrobenzaldehyde, o-nitrobenzaldehyde,5-ethyl-2-thiophenecarbaldehyde, 2-thiophenecarbaldehyde,asaronaldehyde, 5-(hydroxymethyl)-2-furaldehyde,2-benzofurancarboxaldehyde, 2,3,4-trimethoxybenzaldehyde,protocatechualdehyde, heliotropine, 4-ethoxy-3-methoxy benzaldehyde,3,4,5-trimethoxybenzaldehyde, 3-hydroxybenzaldehyde,o-methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxycinnamaldehyde, 2,8-dithianon-4-3n-4-carboxaldehyde, sorbinaldehyde, 2,4-heptadienal,2,4-decadienal, 2,4-nonadienal, 2,4-nonadienal,(E,E)-,2,4-octadien-1-al, 2,4-octadienal, 2,4-dodecadienal,2,4-undecadienal, 2,4-tridecadien-1-al,2-trans-4-cis-7-cis-tridecatrienal, piperonylidene propionaldehyde,2-methyl-3-(2-furyl)acrolein, 2,4-pentadienal, 2-furfurylidenebutyrraldehyde, helional, lyral, 3-hexenal, safranal, veratraldehyde,3-(2-furyl)acrolein, pyruvaldehyde, ethanedial,1-(2,6,6-trimethyl-1-cyclohexenyl)pent-1-en-3-one;4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-Buten-2-one;4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one,5-(2,6,6-Trimethyl-2-cyclohexen-1-yl)4-penten-3-one,(E)-4-(2,2-dimethyl-6-methylidenecyclohexyl)but-3-en-2-one.

Compounds in list (b) are aldehydes and/or ketones which are able toreact with some classes of malodorant compounds, in particular nitrogenbased malodorant compounds, and do not have unpleasant odor.

Reactive compounds in lists (a/a*) and (b) chemically react withmalodors, such as malodorant molecules containing Nitrogen atoms (aminetype odors, typically deriving from the degradation of urine or certainfoods like onions) and/or malodorant molecules containing Sulfur atoms(thiol type malodors, typically associated with protein degradation e.g.in menstrual fluids, feces, food etc) Ammonia/amines are one componentof malodor associated with the absorption of bodily fluids, such asmenses or urine. For example, ammonia/amines are typically present inhigh amounts in absorbent products used for urine absorption due todegradation of urea. Ammonia/amines and their derivatives can react withaldehydes and/or ketones to form imines (according to the so-calledSchiff base reaction).

This reaction is catalyzed by enzymes and/or by a slightly acidic pH 4to 5. The moderate acid requirement is necessary to allow protonation ofthe hydroxyl intermediate to allow water to leave.

Malodorant sulfur based compounds are typically generated by thedegradation of proteins e.g. in menstrual fluids feces or food and sotheir control is particularly important in menstrual absorbent articlessuch as sanitary napkins or pantyliners as well as in other absorbentarticles which get in contact with other proteinaceous materials suchfood residues or feces. The mechanism of action is not fully understoodat the moment, but it is believed that it is connected to the fact thatThiols can react with aldehydes and ketones to form thioacetals andtioketals.

In principle, the chemical reactions described above can be obtainedfrom any aldehyde, but in practice the reactivity of aldehydes in thesetype of reactions and in the specific context of an absorbent article isvery different. The reactive compounds (a) and (b) of the presentinvention are effective in reacting with Nitrogen based malodorantmolecules and those according to (a) are particularly effective inreacting also with sulfur based malodorant molecules.

The particularly high reactivity of these reactive compounds towardssulfur based malodorant molecules renders them effective for use inabsorbent articles which are used to absorb menses.

The preferred reactive compounds of the present invention areparticularly advantageous in the specific context of absorbent articlesbecause they have a pleasant and low intensity odor and are also able tobe complexed effectively and to be quickly released when needed.

Another important aspect of the present invention is that each complexedreactive compound has an individual character in terms of odor.Therefore, their introduction within an absorbent article alsorepresents the possibility to provide not only reactivity on malodorsbut also individual fragrant notes which can be combined with otherodorous components (encapsulated/complexed and/or in free uncomplexedform) thus allowing the formulator to obtain a broader range offragrances being released by the product when used i.e. when thecomplexed reactive compound is activated.

Other odor controlling organic compounds which can be used hereininclude particular other fragrance/masking/reacting components selectedfrom the lists (c), (d) and (e). Components from list (c) are menthol,menthyl acetate, menthyl lactate, menthyl propionate, menthyl butyrrate,menthone, mint terpenes, laevo-carvone, Cis-3-Hexenol & Cis-3-Hexenylacetate, koavone, methyl dioxolan, ethylene brassylate, and salycilateesters. Salycilate esters are preferably selected from amyl salicylate,isoamyl salicylate, isobutyl salicylate, cis-3-hexenyl salicylate, hexylsalicylate, cyclohexyl salicylate, benzyl salicylate, phenylethylsalicylate, propyl salicylate, isopropyl salicylate or mixtures thereof.

These are all compounds which primary function is to mask malodors. Thismay occur through vapor pressure suppression of the malodor or byoverwhelming the unpleasant malodor with the pleasant odor of thefragrance component. These materials, when used, may significantlyreduce the ability to detect the malodors. The masking ability to hidemalodors is possible due to the volatile nature of the materialsselected, which are released from the complex in the absorbent articleand are then inhaled into the nose of a consumer, generally withinsomewhat close range of the absorbent article, e.g. within about 0 to 10meters of the article by normal breathing (although this should in noway be intended to limit the scope of the invention).

Components from list (d) are methyl-dihydrojasmonate, methyl jasmonate,eucalyptol, tetrahydro-linalool, phenyl-ethyl alcohol, hexyliso-butyrate, linalyl acetate, benzyl acetate, Benzyl alcohol, ormixture thereof. These are volatile materials which are well complexedwith cyclodextrin and are released very quickly upon contact with awater based liquid. Their presence allows the absorbent article torespond even more quickly to an insult of malodorant liquid by releasinga compound that have a good general masking effect against malodors, inparticular, being very volatile, reduces the vapor pressure of othermalodorant compounds slowing down their evaporation rate.

List (e) includes other malodor masking and fragrance components whichcan be used s odor controlling organic compounds in the presentinvention:

e) camphor, p-menthane, limonene, cresol, linalool, myrcenol, tetrahydromyrcenol, di-hydromyrcenol, myrcene, citronellol, citronellyilderivatives, geraniol, geranyl derivatives, mugetanol, eugenol, jasmal,terpineol, pinanol, cedrene, damascone, beta pinene, cineole and itsderivatives, nonadienol, ethylhexanal, octanol acetate, methyl furfural,terpinene, thujene, amylacetate, camphene, citronellal,hydroxycitronellal, ethyl maltol, methyl phenyl carbinyl acetate,dihydrocumarin, di-hydromyrcenyl acetate, geraniol, geranial,isoamylacetate, ethyl, and/or triethyl acetate, para-cresol,para-cymene, methyl abietate, hexyl-2-methyl butyrate, hexyl-2-methylbutyrate, and mixtures thereof.

All the compounds mentioned within the present application, unless aspecific isomeric form is specified, also include their isomeric forms,diastereomers and enantiomers.

It may be that, for certain components, the same component can beconsidered both a malodor reactive component, a malodor maskingcomponent, and/or a fragrance component.

In embodiments of the invention wherein one or more odor controllingorganic compounds from the lists above are present the complex can beprepared mixing all compounds together before preparing the complex, or,alternatively, substituted cyclodextrin complexes containing only one oronly some of the compounds can be prepared separately and then mixedaccording to the desires dosages before introduction into the absorbentarticle.

In some embodiments, the absorbent articles of the present invention, inaddition to the components from lists a), b), c), d) and e) in complexedform may also include components from the same lists or other fragrancecomponents in free form or in encapsulated form.

In the present invention, it is however preferred that the absorbentarticle exhibits no noticeable scent (or very little scent) before use.As a result, it is preferred that no or a small level of other fragrantcompounds are present and that the complexed compounds are complexedefficiently and completely so that only a low amount of free componentsare present before product usage and are released only during theutilization of the absorbent article.

The present invention further encompasses a method of reducing malodorassociated with malodorant fluids e.g. bodily fluid such as urine,menses, and/or feces, comprising the step of contacting the fluid withan absorbent article of the present invention. Preferably, the methodreduces the malodor associated with the malodorant fluids.

The present invention also encompasses a method of making an absorbentarticle which comprises the step of applying onto one of the materialsmaking up the article the cyclodextrin complexes according to thepresent invention.

Test Procedures Thiol Vapor Pressure Suppression Index (TVPS)Measurement

Thiol Vapor Pressure Suppression (TVPS) index is a measure of thereduction in butanethiol concentration in the headspace by a compound,as measured using a fast GC instrument, the zNose 7100 (ElectronicSensor Technologies, Newbury Park, Calif.) based on an Surface AcousticWave (SAW) Quartz microbalance detector, or equivalent.

Before any measurements the instrument is calibrated according tomanufacturer's instructions under the same experimental settings. Theinstrument has a DB-5 column (also available from Electronic SensorTechnologies, Newbury Park, Calif.) 1 m in length, 0.25 μm phasethickness, and 0.25 mm in diameter.

For analysis, the zNose is programmed with the Sensor Temperature, InletTemperature, Valve Temperature, and Initial Column Temperature all setto 40° C. The oven is temperature gradient is programmed at a rate of 10C.°/s from 40° C. to a final temperature of 200° C. TVPS of a compoundis measured in the following way: 100 μl±1 μl of a 1% v/v butanethiol(99%, purity, available from Sigma-Aldrich, St. Louis, Mo.) solution inethanol (200 proof) is added into a 1 ml vial (8×40 mm). These vials areborosilcate glass straight walled vial. In another 1 ml vial (8×40 mm),5 μl±0.2 μl of the compound is added. Both open vials are then placedinside a 20 mL headspace vial (22×75 mm), and the vial is immediatelysealed using a screw thread closure with PTFE/Silicone septa. The vialis heated to 37° C. for 4 hours. After 4 hours, the vial is removed fromthe oven and let to equilibrate at 25° C.±2° C. for 15 minutes. Theheadspace inside the vial is sampled using the zNose is sampled for 10 sand analyzed following the experimental protocol outlined above. Sampleswith butanethiol alone, and the volatile active alone, are run using thesame protocol to identify the peaks for both materials. An acceptableretention index for butanethiol is 720±30. If the peaks butanethiol peakand the volatile material peak co-elute, one skilled in the art canmodify the protocol settings to separate those peaks to achieve aminimum resolution of 1.5. For example one can change the columntemperature ramp rate. In between samples, the instrument needs to becleaned to remove any trace materials. To clean the instrument, theinstrument is run without samples as needed until no peaks greater than100 counts are observed.

The amount of butanethiol in the headspace is measured from the area ofthe peak on the chromatograph for butanethiol (A_(BtSH,Rx)). Tocalculate the percentage of butanethiol reduction in the headspace, acontrol with the butanethiol solution without the volatile material isrun in the same manner and the area is measured as well (A_(BtSH,C)).TVPS is then measured as the percentage reduction in butanethiol areacalculated using the following formula:

${TVPS} = {\frac{A_{{BtSH},C} - A_{{BtSH},{Rx}}}{A_{{BtSH},C}} \times 100}$

An example of the type of measurements obtained with the instrument is:

Butanethiol Peak Retention Sample Index Area (counts) ButanethiolControl 720 A_(BtSH,C) = 4934 Vial 1: 100 μl of 1% v/v butanethiol inethanol Vial 2: Empty Butanethiol + Florhydral 720 A_(BtSH,Rx) = 2442Vial 1: 100 μl of 1% v/v butanethiol in ethanol Vial 2: 5 μl Florhydral

Example TVPS Calculation for

${TVPS} = {{\frac{4934 - 2442}{4934} \times 100} = {50.5\%}}$

The value of TVPS for several compounds suitable for the invention ispresented in the table below. TVPS for the compounds indicated with (*)have been approximated using a mathematical model calculated startingfrom real measurements on a large number of compounds. The model iscreated using the QSAR software CAChe ProjectLeader WorkSystem Pro 7.1.Using the molecular structure from the compounds for which TVPS wasevaluated, several molecular properties are calculated. A regressionalgorithm is the used to calculate the best fit to predict TVPS based onthe 4 molecular descriptors that best fit the data. The model is thenused to predict TVPS for other compounds using the same software. Thevalues of TVPS approximated with the molecular modeling system arepresented for illustration only, for the avoidance of doubt it isspecified that the TVPS values for use in the present inventions areonly the TVPS values measured with the zNose analytical method describedabove.

TVPS melonal 20.4 adoxal 24.4 trans-2-hexenal 27.1 ligustral 42.5 FloralSuper 52.4 Florhydral 53.3 5-methyl-2-thiophene-carboxaldehyde 67.4hydratropic aldehyde(*) 72.0 Undecenal(*) 26.2 9-undecenal(*) 67.510-undecenal(*) 52.0 trans-4-decenal(*) 60.3 cis-6-nonenal(*) 57.1isocyclocitral(*) 51.4 precyclemone b(*) 40.7 (E)-2-(z)-6-nonadienal(*)35.8 undecyl aldehyde(*) 34.9 methyl-octyl-acetaldehyde(*) 30.2 Lauricaldehyde(*) 26.6 silvial(*) 25.8 vanillin(*) 23.7 floralozone(*) 23.5Hexylcinnamic aldehyde 8.0 neral 17.1 ethyl vanillin 2.9

Comparison of Fragrance Release of Different Methyl Substitutedβ-Cyclodextrin

To demonstrate the perfume release effectiveness of different methylsubstituted, β-Cyclodextrin (available from TCI America, OR, orequivalent), 2,6-Di-O-methyl-β-cyclodextrin (available from AcrosOrganics, NJ or equivalent), and 2,3,6-Tri-O-methyl-β-cyclodextrin(available from TCI America, or equivalent) were each complexed with amodel blend of Odor Controlling Organic Compounds (indicated with theacronym OCOC) and spiked onto a portion of an ultra, feminine hygienepad (a suitable pad is Always Ultra by Procter and Gamble, orequivalent). The results are shown in the graph of FIG. 2. After dosingwith water the headspace was sampled using Solid Phase Micro-Extraction(a suitable fiber assembly is a 2 cm Stableflex 24 Ga, 50/30 μmDVB/CAR/PDMS available from Supelco, PA or equivalent) followed by gaschromatography/mass spectrometry (a suitable unit is the 5777A MassSelective Detector (MSD) also available from Agilent, or equivalent)with a GERSTEL Multipurpose Sampler (Gerstel, Liticumo, MD orequivalent) to quantify the OCOC release.

The model OCOC used is a neat mixture of benzaldehyde (1.6 g, 15.08mmols), ligustral (1.6 g, 11.58 mmols), citral (1.6 g, 10.51 mmols),cinnamic aldehyde (1.6 g, 12.11 mmols), and florhydral (1.6 g, 8.41mmols). All components are available from Sigma Aldrich, or equivalent.The mixture is homogenized before use.

The Standard Pad Substrates are prepared by cutting a 10 cm lateralstrip across the whole product centered at the longitudinal center of anAlways Ultra normal size pad.

A mixture of the model OCOC for each β-cyclodextrin type was solubilizedin water at a one-to-one molar ratio (β-cyclodextrin/OCOC). The amountof water used for the complexation was adjusted for each β-cyclodextrintype according to its individual water solubility to ensure completedissolution of the β-cyclodextrin complex. Each mixture ofβ-cyclodextrin and OCOC in water was thoroughly homogenized. Solutionsof β-cyclodextrin, OCOC, and water were dosed onto a Pad Substrate. Anamount of solution was added to each pad such that an equivalent of 1 mgof OCOC (complexed by β-cyclodextrin) is available for release uponaddition of water. Pads dosed with the above described solution wereexposed to open air at room temperature for four days to allow water toevaporate leaving only perfume complexed by β-cyclodextrin.Specifically:

Add 555 mg β-cyclodextrin and 68 mg model OCOC to 30 mL of purifiedwater and mixed thoroughly. 810 μL of this solution (adjusted for lossesdue to evaporation) is dosed at the longitudinal and lateral center ofthe pad substrate.

Add 2011 mg 2,6-di-O-methyl-β-cyclodextrin (38.4%) and 210 mg model OCOC(4%) to 3 mL of purified water and mixed thoroughly. 16 μL of thissolution (adjusted for losses due to evaporation) is dosed at thelongitudinal and lateral center of the pad substrate.

Add 1008 mg 2,3,6-tri-O-methyl-β-cyclodextrin (4.8%) and 98 mg modelOCOC (0.46%) to 20 mL of purified water and mixed thoroughly. 452 μL ofthis solution (adjusted for losses due to evaporation) is dosed at thelongitudinal and lateral center of the pad substrate.

The control is prepared by dosing 1.0 mg of the neat OCOC at thelongitudinal and lateral center of the pad substrate. The control isprepared immediately before dosing with the water

The GC analysis was performed on a 30 m long by 0.250 mm diameter columnwith 5% phenyl arylene methylpolysiloxane phase at a 1 μm film thickness(a suitable column is the DBSMS available from Agilent, or equivalentUSP G27 phase). The GC inlet was set at 280° C. in Split-less mode (ACIS-4 SPME low volume glass linear available from Sigma-Aldrich) with a3 mL septum purge. A 1.5 mL column flow of helium was set at an oventemperature of 150° C. under constant flow conditions. The GC oven wasprogrammed to begin at 150° C. for 1 min, then ramp at 16° C./min to230° C., hold for 6 min at 230° C., then ramp at 30° C./min to 300° C.and a final hold of 1 min. Upon injection, the SPME fiber is left in theinjector for 5.00 min.

The temperature for the MSD transfer line and detector were set to 280°C. and 300° C. respectively. The MSD was configured for electronionization at −70 eV scanning from 35 m/z to 300 m/z with a scan rate of192 msec/scan. A Total Ion Chromatogram (TIC) is collected for eachspecimen. The TIC is then processed to extract ion chromatograms at 106m/z (benzaldehyde), 67 m/z (ligustral) 69 m/z (citral), 131 m/z(cinnamic aldehyde) and 105 m/z (forhydral). The peaks of interest inthe extracted ion chromatogram are integrated and summed.

Each absorbent article Specimens was placed in a 250 mL glass jar andsealed with a PTFE/silicone septum lid (fluoropolymer resin-lined,available from I-CHEM, Thermo Scientific, or equivalent). The pad ispositioned along the wall of the jar with the back sheet against thewall. The jar is placed on its side and rotated such that thelongitudinal center of the substrate can be dosed with 1.00 mL ofpurified water. The jar is sealed and the headspace sampled using theSPME for 30 sec at 5, 10, and 30 minute time points after the additionof water. The control is analyzed in like fashion for comparison.

The % Release is based on the summed area of the peaks of interestwithin the extracted ion chromatogram, normalized to the applied mass ofthe cyclodextrin: % Release=(Summed Area Counts of β-cyclodextrin/SummedArea counts of control)/mg of β-cyclodextrin dosed on pad

In like fashion, three replicates of each β-cyclodextrin complex andcontrol are analyzed and the % Release is calculated for each. The %Release is reported as the arithmetic mean of the three replicates tothe nearest 0.1%/mg. Results are graphed in FIG. 2 showing perfumerelease from pads per mg dimethyl- and trimethyl-β-cylclodextrin versusunderivatized β-cyclodextrin. As shown in the graph of FIG. 2, theinventors have surprisingly found that 2,6-dimethyl-β-cyclodextrinprovides a much higher percent release of fragrance than doesconventional β-cyclodextrin. Similarly, 2,6-dimethyl-β-cyclodextrin alsoprovides a much higher release of fragrance than does 2, 3,6-trimethyl-β-cyclodextrin. As shown, in some forms, the substitutedcyclodextrin complexes of the present invention may provide a percentfragrance release of greater than about 200 percent of that ofconventional β-cyclodextrin after 10 minutes. In some forms, thesubstituted cyclodextrin complexes of the present invention may providea percent fragrance release of greater than about 300 percent of that ofconventional β-cyclodextrin after 10 minutes, greater than about 400percent after 10 minutes, greater than about 500 percent after 10minutes, greater than about 500 percent after 20 minutes, or greaterthan about 500 percent after 30 minutes, specifically reciting allvalues within these ranges and any ranges created thereby.

Effectiveness of Location of Substituted Cyclodextrin Complex

The effectiveness of the MBCD complex within an absorbent article wasanalyzed by headspace solid-phase microextraction (SPME) followed by gaschromatography/mass spectrometry.

The GC analysis was performed on a 30 m long by 0.250 mm diameter columnwith 5% phenyl arylene methylpolysiloxane phase at a 1 μm film thickness(a suitable column is the DBSMS available from Agilent, or equivalentUSP G27 phase). The GC inlet was set at 280° C. in Split-less mode (ACIS-4 SPME low volume glass linear available from Sigma-Aldrich) with a3 mL septum purge. A 1.5 mL column flow of helium was set at an oventemperature of 60° C. under constant flow conditions. The GC oven wasprogrammed to begin at 60° C. for 1 min, then ramp at 10° C./min to 215°C., then ramp at 25° C./min to 315° C. and a final hold of 2.5 min. A 24gauge SPME fiber assembly (50/30 μm DVB/CAR/PDMS, Stableflex 2 cm fiber)is used to collect headspace. Upon injection, the SPME fiber is left inthe injector for 1 min followed by a 1.0 min post extraction of theheadspace above an external standard solution consisting of ethyllinalool solubilized in 3 mL of a 12% sodium dodecyl sulfate solution ata concentration of 1000 parts per million (ppm).

The temperature for the MSD transfer line and detector were set to 230°C. and 40° C. respectively. The MSD was configured for electronionization at −70 eV scanning from 35 m/z to 400 m/z with a scan rate of1424 amu/sec and a minimum threshold signal of 250 counts. A Total IonChromatogram (TIC) is collected for each specimen. Analyte signal areasare ratioed to the peak area of the external standard.

A specimen is collected as die cut a circular 4 cm diameter (12.57 cm²)specimen from the article at the region of interest, e.g. target zonedescribed heretofore. The specimen contains all layers of the article.The specimen can be measure intact or sub-sectioned in the z-direction(see FIG. 5) into individual layers. Each specimen was placed in a 125mL specimen jar (e.g. EPA Clear Wide-Mouth Septa Jars, VWR part #UX-99540-21, with PTFE-lined Silicone septum, VWR part #1BT58-400W0T, orequivalent). 3.0 mL of Millipore purified water, is added to a specimenand the jar is sealed for 4.0 hours at room 23° C. before sampling.Relative fragrance intensity differences between each unique sample weremeasured via SPME-GC/MS as described above.

As an illustration of MBCD/perfume presence on different layers of anarticle, a Pampers Swaddler diaper (Article A) was made in parallel to adiaper identical with the exception that no SAP was added to the core(Article B).

A test perfume consisting of beta gamma hexenol (CAS#928-96-1),d-limonene (CAS#5989-27-5), eucalyptol (CAS#470-82-6), phenyl ethylalcohol (60-12-8), florhydral (CAS#125109-85-5), and flor acetate(CAS#5413-60-5) is prepared. The MBCD/perfume dose solution is a mixtureof Millipore purified water (2 g, 28.4 wt. %), ethanol (2 g, 28.4 wt.%), methylated β-cyclodextrin (CAVASOL® W7 M from Wacker Chemie AG, 2.67g, 37.8 wt. %), and perfume, (381 mg, 5.4 wt. %). MBCD solutions arenebulized using an X-175 Nebulizer (175 μm capillary) (BurgenerResearch, Mississauga, Ontario, Canada, or equivalent), with a 40 PSInitrogen back pressure. The solutions are introduced into the nebulizerat a specified flow rate using a syringe pump (e.g. Cole-Parmer 74900series single-syringe infusion pump, or equivalent).

MBCD/perfume treated SAP was prepared by nebulization of theMBCD/perfume onto the SAP and by swelling the SAP with an aqueousMBCD/perfume mixture.

Nebulization on SAP: 10 g of particulate SAP (available from NipponShokubai) was distributed evenly over the bottom of a 100 mm diameterglass petri dish. 20 μL of the MBCD/perfume dose solution (approximately1.1 mg perfume) was nebulized uniformly over the surface of the SAP. Thenebulizer was held approximately 8 cm above the SAP and mixture wasdeposited at 20 μL min⁻¹ for 1.0 min. Spray-coated AGM was dried at roomtemperature for 15 min then transferred to a 40 mL glass vial, capped,and shaken vigorously by hand for 30 seconds to thoroughly mix the SAPparticles.

Swelling of SAP: 10 g of particulate SAP (available from NipponShokubai) is placed into a 500 mL glass beaker. 20 μL of theMBCD/perfume dose solution (approximately 1.1 mg perfume) is added to 75mL of Millipore purified water and mixed thoroughly. All 75 mL is addedto the beaker and the SAP is allowed to completely absorb the mixture.The swelled material was distributed evenly within a 190×100 mm glasspetri dish and placed in an oven at 100° C. for 2 hours to dry.

Article A is prepared by die cutting a circular 4 cm diameter (12.57cm2) specimen from the article at the longitudinal and lateral center ofthe article. The specimen contains all layers of the article. Fivespecimens are prepared for each layer to be tested. For the topsheet,the nebulizer was positioned 4 cm above the center of the specimen. Thespecimen was rotated at a rate of 100 to 200 rpm as 0.9 μL of theMBCD/perfume dose solution was nebulized onto the surface at a rate of10 μL min′. Specimen is set out on the benchtop and allowed to dry for15 minutes at room temperature before placing into a 125 mL specimen jar(e.g. EPA Clear Wide-Mouth Septa Jars, VWR part # UX-99540-21, orequivalent).

Specimens from additional Article A samples are prepared dosing otherlayers from the article, for this example the Acquisition Layer (AQL)and the non-woven core cover (NWCC). For the AQL, the top sheet isremoved from the specimen and set aside. The surface of the AQL is thendosed in like fashion to the top sheet. After drying for 15 minutes thetop sheet is replaced before sealing it into a specimen jar. The sameprocedure is repeated for the NWCC.

To evaluate the effectiveness of MBCD deposited on SAP, die cut acircular 4 cm diameter (12.57 cm2) specimen from the article at thelongitudinal and lateral center of Article B. Remove all layers abovethe NWCC and place 472 mg of the spray coated SAP prepared above.Replace the upper layers of the specimen and place into a 125 mLspecimen jar.

Specimens are then analyzed using the SPME/GC/MS method as describedabove.

Extraction of MBCD from Absorbent Articles

MBCD can be collected from whole articles or components by Soxhletextraction with water and the subsequent removal of solvent (water)using a rotary-evaporator. For further analysis of methyl substitution,enough articles need to be extracted to collect 50 mg of MBCD.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. An absorbent article comprising a topsheet, a backsheet, and an absorbent core disposed between the topsheet and the backsheet, the absorbent article further comprising: providing a solution in a solvent system said solution comprising a cyclodextrin comprising an odor controlling organic compound wherein said cyclodextrin is a substituted cyclodextrin (wherein the H atom of OH groups in positions 2, 3 and 6 is partially or entirely replaced by a substituent —R) having a substitution degree (DS) of 0.4 to 2.5 —R substituents per glucose unit of cyclodextrin and wherein substitution in position 2 is about 20 percent or above, in position 6 is about 20 percent or above and in position 3 is less than the degree of substitution in positions 2 and/or position 6, and wherein the substituted cyclodextrin complex is disposed in the absorbent core.
 2. The absorbent article of claim 1, wherein substitution in position 3 is less than 50 percent, preferably less than about 40 percent, more preferably less than about 30 percent, most preferably less than about 20 percent.
 3. The absorbent article of claim 1, wherein the substitution in position 3 is less than about 40 percent.
 4. The absorbent article of claim 1, wherein the substitution in position 3 is less than about 30 percent.
 5. The absorbent article of claim 1, wherein the substituted cyclodextrin complex has a substitution degree of from between about 0.9 and about 2.4,
 6. The absorbent article of claim 1, wherein the substituted cyclodextrin complex has a substitution degree of between about 1.2 and about 2.2.
 7. The absorbent article of claim 1, wherein the substituted cyclodextrin complex has a substitution degree of between about 1.6 and about 2.1.
 8. The absorbent article of claim 1, wherein the substitution in position 2 is between about 20 percent and about 90 percent.
 9. The absorbent article of claim 1, wherein the substitution in position 2 is between about 45 percent to about 80 percent.
 10. The absorbent article of claim 1, wherein the substitution in position 6 is between about 20 percent and about 90 percent.
 11. The absorbent article of claim 1, wherein the substitution in position 6 is between about 40 percent and 80 percent.
 12. The absorbent article of claim 1, wherein the —R substituents are selected from linear or branched C1-C5 saturated chain.
 13. The absorbent article article of claim 1, wherein the —R substituents are selected, from methyl and hydroxymethyl and are preferably methyl.
 14. The absorbent article of claim 1, wherein the absorbent article further comprises an overall length generally parallel to a Y-axis and an overall width parallel to an X-axis, wherein the substituted cyclodextrin complex is provided in a target zone (330) of the absorbent article.
 15. The absorbent article of claim 14, wherein the target zone is disposed between two outer zones (335), and wherein the target zone comprises more than about 20 percent to less than about 80 percent of the overall length of the absorbent article.
 16. The absorbent article of claim 14, wherein the target zone is disposed between two outer zones (335), and wherein the target zone comprises more than about 30 percent to less than about 70 percent of the overall length of the absorbent article.
 17. The absorbent article of claim 14, wherein the target zone is disposed between two outer zones (335), and wherein the target zone comprises more than about 40 percent to less than about 60 percent of the overall length of the absorbent article.
 18. A method to manufacture an absorbent article the method comprising: providing a solution in a solvent system said solution comprising a cyclodextrin comprising an odor controlling organic compound wherein said cyclodextrin is a substituted cyclodextrin (wherein the H atom of OH groups in positions 2, 3 and 6 is partially or entirely replaced by a substituent —R) having a substitution degree (DS) of 0.4 or to 2.5 —R substituents per glucose unit of cyclodextrin and wherein substitution in position 2 is about 20 percent or above, in position 6 is about 20 percent or above and substitution in position 3 is less than that of position 2 and/or position 6; providing a material component comprised by the absorbent article; and applying an amount of the solution to the material component of the absorbent article in a target zone and wherein the substituted cyclodextrin is disposed in the absorbent core.
 19. The method of claim 18, further comprising the step of evaporating the solvent and precipitating the cyclodextrin complex on the material component of the absorbent article or spraying the solution onto the material component of the absorbent article.
 20. The method of claim 18, wherein the absorbent article further comprises an overall length generally parallel to a Y-axis and an overall width parallel to an X-axis, wherein the target zone is disposed between two outer zones, and wherein the target zone comprises more than about 20 percent to less than about 80 percent of the overall length, more preferably more than about 30 percent to less than about 70 percent, most preferably more than about 40 percent to less than about 60 percent of the overall length. 